Process for the production of multi-colour effects on natural and synthetic polyamide fibre material

ABSTRACT

A dyeing process for the production of multi-colour effects on natural and synthetic polyamide fibre material, as well as the multi-coloured fibre material produced thereby, which process consists of pretreating the fibre material with an aqueous solution of at least one colourless, fibre-reactive compound and optionally with one levelling agent having affinity for the fibre material, combining the treated material with untreated fibre material and/or with at least one fibre material pretreated in a different manner, and dyeing the combined fibre material with a dyestuff having affinity for the fibre material or with a mixture of such dyestuffs, said process being characterized in that the colourless, fibre-reactive compound contains per molecule thereof at least one group of the Formula I

nited States Patent [191 uehler et a1.

1451 Nov. 27, 1973 1 PROCESS FOR THE PRODUCTION oF MULTl-COLOUR EFFECTS ON NATURAL AND SYNTHETIC POLYAMIDE FIBRE MATERIAL [75] Inventors: Arthur Buehler, Rheinfelden;

Walter Moslmann, Therwil, both of Switzerland [73] Assignee: Clha-Gelgy AG, Basel, Switzerland 22 Filed: June a, 1971 [21] Appl. No.: 150,930

[30] Foreign Application Priority Data June II, 1970 Switzerland 8809/70 52 us. Cl. 8/15, 8/1 A, 8/21 R 51 Int. Cl. D06p 3/04, D06p 3/24 581 Field of Search 8/15, 21, 31, 18,

s/65,.1 A, 1 E

[56] References Cited UNITED STATES PATENTS 3,232,692 2/1966 Wilhelm et al. 8/18 3,494,717 2/1970 Wegmann et al 8/31 FOREIGN PATENTS OR APPLICATIONS l,l89,726 4/l970 Great Britain 8/18 484,321 2/1970 Switzerland 8/18 1,573,425 7/1969 France Primary Examiner-Leon D. Rosdol Assistant Examiner-T. J. Herbert, Jr. Attorney-Harry Goldsmith, Joseph G. Kolodny and Mario A. Monaco [5 7 ABSTRACT A dyeing process for the production of multi-colour effects on natural and synthetic polyamide fibre material, as well as the multi-coloured fibre material produced thereby, which process consists of pretreating the fibre material with an aqueous solution of at least one colourless, fibre-reactive compound and optionally with one levelling agent having affinity for the fibre material, combining the treated material with untreated fibre material and/or with at least one fibre material pretreated in a different manner, and dyeing the combined fibre material with a dyestuff having affinity for the fibre material or with a mixture of such dyestuffs, said process being characterized in that the colourless, fibre-reactive compound contains per molecule thereof at least one group of the Formula I NI-I CO R wherein R represents either C=CH1 or CIICH1 Br r r or of Formula II N/ 0Cl NHHJ\ /BF bound to an aromatic carbon atom, said fibre-reactive compound serving as reserving agent.

32 Claims, No Drawings The present invention concerns a dyeing process for the production of multi-colour effects on natural and synthetic polyamide fibre material, as well as the multicoloured fibre material produced thereby.

It is known, e.g. from Swiss Pat. No. 484,321, to reserve portions of natural polyamide textile fibre material against anionic dyestuffs by impregnating the desired places with pastes containing in solution or dispersion one or more colourless fibre-reactive compounds which contain no basic groups and fixing the impregnation, i.e. printing the textile material, e.g. wool.

Synthetic polyamide material has already been reserved using colourless fibre-reactive compounds, in which compounds however the fibre-reactive group must be bound to the rest of the molecule of the reserving agent via an -SO --bridge (cf. British Pat. No. 1,189,726).

A process has now been found by which it is possible to permanently reserve not only natural but also synthetic polyamide fibre material, not only by printing but also by the padding method and the cold-storage process, and even by the exhaustion process. The present invention has a large range of possible applications. This process makes possible hitherto unattainable contrast effects on natural and synthetic polyamide fibre material in the most diverse conditions during its processing. In contrast to the hitherto known printing process, the variety of possible patterns is practically unlimited.

A further important advantage of the present invention is that the amount of the reserving agent used which is fixed on the fibre is substantially higher than with previously known reserving agents.

In the process according to the invention the polyamide material is first pretreated with an aqueous solution of at least one colourless fibre-reactive compound and preferably with a levelling agent, then combined with untreated fibre material and/or with at least one fibre material pretreated in a different manner, and then dyed with a dyestuff or mixture of dyestuffs having affinity for the fibre material. Since the colourless fibrereactive compounds according to the invention are fixed permanently on the fibre material, it is possible in this manner to obtain very beautiful multi-colour effects, e.g. tone-in-tone dyeings, i.e. dyeings which have the same colour in various tones. The portion which has been impregnated with the reserving agent according to the invention has a lighter shade than the untreated portion.

The process according to the invention is characterised in that the colourless, fibre-reactive compound contains per molecule thereof at least one group of the Formula I NHCO--R wherein R represents either or of Formula II F 5 N/ C-Cl -NH-i:\ -F

bound to an aromatic carbon atom, said fibre-reactive compound serving as reserving agent.

By colourless, fibre-reactive compounds are meant colourless organic compounds containing reactive groups which readily react with the fibre substrates, i.e. such which can form a covalent chemical bond.

Aromatic radicals of these compounds can contain additional substituents such as, e.g. halogen atoms, hydroxyl groups, and low-molecular alkyl and alkoxy groups.

The colourless, fibre-reactive compounds according to the invent are water-soluble. Suitable watersolubilising groups are, e.g. carboxylic acid groups, acid sulphuric acid ester groups and phosphoric acid ester groups, phosphoric acid groups, acylated sulphonic acid amide groups, and in particular, sulphonic acid groups. Particularly advantageous are compounds containing at least one sulphonic acid group. The term sulphonic acid group or carboxyl group embraces the free acid, and also salts of these acids, as well as the dissociated state of the acids.

The colourless fibre-reactive compounds according to the invention are produced according to known methods.

Preferred as reserving agents are the colourless fibrereactive compounds of the Formula III AD(BD),,A

(Ill) wherein A represents a group of the Formula I or, when n is l, B is CI-I=CH and SOJH,

D is

also a group of the Formula II;

B represents a direct bond, or the bridge member -C I-I=CI-I-- or (E i NH E l'; NH N D represents a benzene or naphthalene radical containing at least one sulfo group; and n represents zero or the integers l, 2 or 3.

Particularly valuable are the colourless fibre-reactive compounds of Formula III in which B represents the bridge member CH=CI-l--, D represents a benzene radical containing a sulfo group and n represents the number 1.

The colourless, reactive compounds are applied from aqueous preparations to the polyamide fibres. Suitable natural polyamide fibre is, in particular, wool. Synthetic polyamide fibres are obtained, for example, from the polycondensation products of adipic acid and hexamethylenediamine (Nylon 6.6), and sebacic acid and hexamethylenediamine (Nylon 6, or from the polymerisation products of e-caprolactam (Nylon 6), or w-aminoundecanoic acid (Nylon 1 l The reactive compounds can be applied to the fibre material by known methods, e.g. by the exhaust or impregnation process, whereby the whole substrate is subjected to a uniform treatment.

In the case of the exhaust process, the operation is performed in aqueous baths at temperatures of from 80 to 110C, preferably at 90 to 100C; the pH-value of the preparations is 4 to 7, preferably 4 to 6, and is adjusted, if necessary, with organic acids. Suitable organic acids are such having one to four carbon atoms, especially formic and acetic acid. Additionally, the preparations can contain further agents, such as e.g. salts, or surface-active agents such as wetting and dispersing agents. Suitable ratios of goods to liquor are between 1 10 and l 40.

The impregnating baths, which can also be in a coazervated form, contain approximately the same additives and, optionally, also thickeners. The impregnating process can be carried out, for example, on a padding machine, at temperatures between and 40C.

The fixing of the fibre-reactive compounds is effected by a cold-storage process of, e.g., 2 to 48 hours duration at room temperature, or by a short duration steaming process. The substrate is then washed, and dyed in admixture with fibre material of a different type. The fibre-reactive compounds are so fixed on the fibre that they are fast to boiling.

The amounts in which the colourless, fibre-reactive compounds can be used can vary within wide limits, and are adjusted according to the desired depth of colour of the multicolour effects, and also according to the dyestuffs used. Suitable amounts are about 0.1 to 10 percent by weight, preferably 0.2 to 2 percent by weight, for synthetic polyamide fibre material, and l to 6 percent by weight for W001, relative to the fibre material.

The material treated according to the invention with the colourless, fibre-reactive compounds, the said material being preferably in loose form as slubbing or yarn, is then combined with material not pretreated and/or with at least one fibre material pretreated in a different manner, the combining of the materials being effected, e.g. by mixing, carding, twisting, weaving, embroidering, or knitting.

By the term pretreated in a different manner" is meant that material is used which has been pretreated either with another fibre-reactive compound, or with different concentrations of the same compound.

Optionally, the polyamide fibre material pretreated according to the invention can be combined not only with untreated and/or differently pretreated polyamide fibre material, but also with other organic fibres, e.g. with cellulose fibres, especially cotton, polyester or polyacrylonitrile fibres. In the subsequent dyeing process suitable dyestuffs having affinity for the fibre should be used.

The obtained fibre mixtures are then dyed in the next stage of the process with a dyestuff or dyestufi' mixture having affinity for the fibre, the dyeing being performed in the usual manner, advantageously in the presence of the usual dyeing auxiliaries.

The usual dyeing auxiliaries are, e.g., condensation products from fatty amines and ethylene oxide, which can be, in addition, quaternised and/or esterified; fatty alcohol/ and alkylphenol/ethylene oxide addition products, which can, optionally, likewise be esterified, and condensation products of fatty acids with lower alkanolamines, as well as polyglycol ethers of these condensation products.

Suitable as dyestuffs for the process according to the invention are the usual anionic wool dyestuffs which can belong to very diverse classes of dyestuffs. These can be, for example, the commercially important dyestuff classes of the azo, anthraquinone, phthalocyanine, nitro or formazane dyestuffs which can also contain metals bound in complex linkage such as copper, nickel, chromium or cobalt. Suitable azo dyestuffs are, principally, monoazo dyestuffs, e.g. of the type phenylazobenzene, phenylazonaphthalene, phenylazohydroxyor -aminopyrazole, phenylazoacylacetylarylamide, or those of the analogous naphthylazo series, whereby the aromatic nuclei can be suitably substituted. Also suitable are disand polyazo dyestuffs. The azo dyestuffs, to which also belong the formazane dyestufis, can be metallised, principally by chromium or cobalt, but also by copper or nickel, whereby one or two dyestuff molecules per metal ion participate in the complex. In addition to the usual substituents such as halogen, nitro, acylamino, alkyl, alkoxy and sulfonyl, etc., the anionic wool dyestuffs which can be used according to the invention can in particular also contain substituents which have affinity to the fibre material, for example substituents having a portion which can be split off as an anion, e.g. mobile fluorine, chlorine, or bromine atoms or sulfo-oxy groups, or double bonds which are capable of addition such as vinyl sulfonyl or vinyl carbonyl groups, or both types of reactive configurations such as in a,B-dichloroor dibromo-acroylamino groups. From the standpoint of dyeing, both those classes of anionic wool dyestuffs which are strongly acid as well as those which dye weakly acid to neutral are suitable.

Especially preferred are the reactive dyestuffs which are derived, in particular, from water-soluble azo and anthraquinone dyestuffs, and contain, as reactive grouping, at least one acylamino radical derived from an a,B-unsaturated aliphatic carboxylic acid containing one to four carbon atoms, or at least one radical convertible by the elimination of acid into such an acylamino radical. Examples of reactive groupings are the radical derived from acrylic acid of the formula CH CH CO (IV) wherein X represents in each case a chlorine or bromine atom.

The reactive groupings are preferably bound by way of a nitrogen atom to an aromatic ring of the dyestuff molecule. The dyestuffs contain as suitable watersolubilising groups, e.g. carboxylic acid groups or sulphonic acid groups. Preferred are such dyestuffs containing at least one sulphonic acid group.

If only one single dyestuff is used in the dye bath, then multi-colour effects varying only in shade are obtained on the polyamide fibre mixture. Particularly valuable multi-colour effects are obtained, however,

with the use of two or more dyestuffs of varing shades.

The polyamide fibre mixture can be dyed in the most diverse conditions during its processing, thus, for example, in loose form or as slubbing, tow, yarn, fabric, knitware, fibre-fleece, or carpet.

The dyeing is performed in the exhaust process (ratio of goods to liquor ca. 1 20 to l 50) by known methods at temperatures of from 80 to l C, preferably 90 Br Br to 100C; or in the impregnating process on a padding machine at room temperature, whereby fixing of the dyestuff on the fibre is afterwards effected by a shortduration steaming process, or by storage at room temperature for a fairly long period of time, tag. 2 to 48 hours.

The dye bath can also contain the auxiliaries usual in the dyeing industry, e.g. salts such as sodium sulphate or ammonium sulphate, acids such as acetic acid or formic acid, wetting agents or surface-active compounds as levelling agents, non-ionic compounds, e.g. urea or thiourea, and, optionally, thickeners, the lastmentioned being used especially in the impregnating liquors.

The pl-l-values of the dyeing preparations are be tween 4.5 and 6.5, and are adjusted with low-molecular acids, preferably with formic or acetic acid.

it is particularly advantageous, in the pretreatment and in dyeing, to employ a levelling agent having affinity for the fibre, thus increasing the contrast effects.

In a preferred embodiment of the process according to the invention, in the pretreatment bath for the reservation of wool there are employed from 2 to 6 percent of a colourless fibre-reactive compound according to the invention, relative to the weight of the goods; 1 percent of an auxiliary consisting of a. 1 part of the adduct from 1 mol of a fatty amine (30 percent of hexadecylamine, 25 percent of octadecylamine and 45 percent of octadecenylamine) and 7 mol of ethylene oxide, quaternised with chloroacetamide, and

b. 1 part of the ammonium salt of the acid sulphuric acid ester of the unquaternised adduct a;

and 2 to 2.5 percent of acetic acid (80 percent); and in the pretreatment bath for the reservation of synthetic polyamide material there are employed from 0.2 to 2 percent of a colourless fibre-reactive compound according to the invention; 2 percent acetic acid (80 percent), and optionally 1 percent of the above-defined auxiliary mixture.

The process according to the invention enables twoor multi-colour effects to be obtained on undyed fibre materials by dyeing in one dye bath, using one or more dyestuffs. The colourless, fibre-reactive compounds are so fixed on the fibre that they are fast to boiling, so that, in the actual dyeing process, no migration of these compounds on to the untreated material can occur. A

levelling out of the two or multi-colour effects is thus avoided. The process is simple to perform, and a minimum of operational stages is required for the process. No damage to the fibres occurs either during the pretreatment of during the actual dyeing process.

In the following examples the temperatures are given in degrees centigrade.*Parts are parts by weight and percentage figures are percent by weight, calculated on the weight of the fibre material employed unless otherwise expressly designated. The ratio of goods to liquor is given in parts by volume.

Example 1 100 parts of wool yarn are treated for one hour at 100 in an aqueous preparation (ratio of goods to liquor 1 40) containing 6 percent of the colourless, fibre-reactive compound of the formula Br Br S0311 A 2.5 percent of acetic acid percent), and 1 percent of an auxiliary mixture consisting of a. 1 part of the adduct from 1 mol of a fatty amine (30 percent of hexadecylamine, 25 percent of octadecylamine and 45 percent of octadecenylamine) and 7 mol of ethylene oxide, quaternised with chloroacetamide, and b. ,1 part of the ammonium salt of the acid sulphuric acid ester of the unquaternised adduct a. The wool yarn is afterwards rinsed, and then dyed for 1 hour at 100 together with 100 parts of untreated wool yarn in a dye bath (ratio of goods to liquor 1 40) containing 0.75 percent of the blue dyestuff of the formula O NH:

ll l A sour SOaH y I Br d) HN -NHC 0 -C=CH2 0.5 percent of the above-given auxiliary mixture, and an amount of acetic acid (80 percent) sufficient to obtain a pH-value of the dye bath of 5.5.

The fibre material is wetted for 5 minutes at 50 in a preparation containing the auxiliary and the acid; the dyestuff is then added, the whole heated in 50 minutes to boiling, and dyeing carried out for 1 hour at this temperature. After cooling of the dye bath to 80, the pH- value is adjusted with ammonia to 8.5, and the fibre material then treated for 15 minutes. The dyed material is subsequently rinsed and dried.

The untreated yarn has been dyed blue, while the treated yarn displays a level light blue shade.

The goods to liquor ratio may vary between 1 l0 and l 40. A similar dyeing is obtained when the dyebath is heated to and dyed for minutes at this temperature.

If in the example above only 3 percent instead of 6 percent of the colourless fibre-reactive compound is used, a similar dyeing is obtained, the contrast being somewhat weaker. V

When the auxiliary mixture is omitted in the pretreatment, the contrast between the treated and untreated wool in the subsequent dyeing is not as strong. Example 2 100 parts of wool yarn are treated for one hour at and 0.6 percent Of the blue dyestuff given in Example 100 in an aqueous preparation (ratio of goods to lithe Untreated P has been y d gr y, While t e quor l 40) containing 6 percent of the colourless, treated part has a level light grey shade. fibre-reactive compound of the formula Example 4 c1 5 If the dyestuff in Example 1 is replaced by 1 percent of the dyestuff of the formula $03K 50 11 N CH: HNJ7 CHN CH=CH I 10 IT'H -cm NHCOCHCH l I CH3 S OJH Br Br i (Ill-Ia SOaH SOBH 5 0 HI I-QCI-Ia 2 percent of acetic acid (80 percent), and 1 percent of as well as 2 percent of acetic acid (80 percent), the unthe auxiliary mixture given in Example 1. The wool treated part has been dyed blue, while the treated part yarn is afterwards rinsed, and then dyed for 1 hour at has a level light blue shade.

lOO", together with 100 parts of untreated wool yarn in Ex mple 5 a dyebath (ratio of goods to liquor 1 I Containing If the dyesutff in Example 1 is replaced by a mixture Percent of the red dyestuff of the formula of 0.5 percent of the yellow dyestuff of the formula so r! HO NH-CO -NHCO-CHCH2 if C[JHaC|IHCOI IH Hmsk S0311 Br Br 7 0.5 percent of the above-given auxiliary mixture and OH sufficient acetic acid (80 percent) to give the dyebath OH 64311; a pl-l-value of 5.5.

The fibre material is after-treated as given in Exam- N NC\ I ple l. The dyed goods are then rinsed and dried.

The dyeing has good fastness properties, especially good wetfastness. 40 Oz-NH-CHa The untreated yarn has been dyed red, while the 1:2 cobalt complex treated yarn has a level light pink shade. Example 3 if the dyestuff in Example 1 is replaced by a mixture percem of the bordeaux dyestuff of mg. @rmula of 0.12 percent of the yellow dyestufi of the formula OH OH I CH: 1 NH-CHg-CI-Ir-O CH; 1:2 cobalt complex Br and 0.2 percent of the grey dyestuff of the formula 0.3 percent of the red dyestuff of the formula OH OH HQN l! r I 0 CH;

O NIT-CH3 1:2 chromium complex as well as 1.5 percent of acetic acid percent), the

WHO! untreated part has been dyed brown, while the treated part has a level light brown shade. cm Example 6 W001 slubbing is padded with the following preparation, and then squeezed out to 100 percent weight increase:

60 parts of the colourless compound of the formula 30 parts of the ammonium salt of the acid sulphuric acid ester of the addition product of 2 mol of ethylene oxide with 1 mol of p-tert. nonylphenol,

320 parts of a 2.5 percent aqueous solution of a starch/ether thickening, and

parts of acetic acid (80 percent),

made up to 1,000 parts with water. The pH-value of the 50 parts of the thus pretreated fabric and 50 parts of untreated fabric are dyed by the exhaust process at 100 with a dye liquor having, with a goods/liquor ratio of l 40, the following composition:

0.9 percent of the yellow dyestuff given in Example 3, 1.1 percent of the red dyestufi' given in Example 3, 0.45 percent of the blue dyestuff of the formula 0 NHz SOaH preparation is 5. The fibre material is subsequently Hots sOiH Br steamed for 45 minutes at 100, and then rinsed. 1 I

For dyeing, 50 parts of pretreated slubbing and 50 HN a parts of untreated slubbing are mixed, and the whole is y for 1 hour at boiling temperature with the 0.5 percent of the auxiliary mixture given in Example dyestuff according to Example 2. 1 d

After the cooling of the dye bath to 80, the pH-value 2,0 percent of acetic acid (80 percent). is adjusted with ammonia to 8.0, and the fibre material Th l-L l f th d li is 5,0 Aft r d in th is treated for 15 minutes. The dyed material iS subsedye liquor is adjusted with ammonia to a pH-value of quently rinsed, and then dried. 8.5, and the fibre material treated therein for 15 min- Th ntreated slubbing has been dyed red, whilst the utes at 80; the material is afterwards rinsed and dried. untreated slubbing displays a light pink shade. The treated fibre material and the untreated fibre A similar dyeing is obtained when the above-given material display varying shades of brown (two-tone efcolourless fibre-reactive compound is replaced by the feet). following compound: Example 8 F F 014/ \N 80311 N/ CCl as. i c..=cfi@ m i a.

Example 7 100 parts of polyamide-6.6-yam (Nylon yarn) are Wool fabric is padded with the following preparation, and squeezed out to 100 percent weight increase: 300 parts urea, 320 parts of a 2.5 percent aqueous solution of a starch/ether thickening, 10 parts of the reaction product of coconut oil fatty acid with 1 mol of diethanolamine, 30 parts of the colourless compound of the formula SOaH 2 parts of acetic acid (80 percent),

made up to [,000 parts with water. The pH-value of the preparation is 5.5. The impregnated fibre material is then stored for 48 hours at room temperature with the exclusion of air, and afterwards rinsed.

treated, with a ratio of goods to liquor of l 40, for 1 hour at 100 with a liquor containing 1.0 percent of the colourless compound given in Example 1, and 2.0 percent of acetic acid (80 percent).

The yarn is subsequently rinsed. The goods/liquor ratio can be varied between 1 l0 and l 40. The exhaust process may also be carried out for 30 minutes at 105.

50 parts of pretreated polyamide yarn are combined with 50 parts of untreated polyamide yarn to a knitted fabric and dyed for 1 hour at 100 with an aqueous dyebath containing 0.3 percent of the yellow dyestuff given in Example 0.2 percent of the blue dyestuff given in Example 1, and

2 percent of acetic acid percent) in a goods to liuor ratio of l 40 at a pH-value of the dyebath of 5. A usual levelling agent can be added to the dyebath in order to avoid any occurrence of streakiness of the polyamide fibre material.

A knitted fabric is thus obtained having a green twoshade efiect.

Example 9 NaOOC less compound of that example is replaced by 0.5 percent of the colourless compound of the formula Br Br Br Br and the dyestuff mixture is replaced by 0.5 percent of the dyestuff given in Example 2; the untreated part has been dyed red, while the treated part has a level light pink shade. Example 10 Employing the procedure of Example 8, the colourless compound of that example is replaced by 1.5 percent of the colourless compound of the formula SOaH r rBr and the dyebath is replaced by 1 percent of the grey dyestuff given in Example 5 and 3 percent of ammonium sulfate; the untreated part has been dyed grey, while the treated part has a level light grey shade. Example 12 Similar results are obtained when the colourless fibre-reactive compound given in Example 8 is replaced by 1 percent of the colourless compound of the formula SOall IIN Hoa

and the dyebath is replaced by 1 percent of the dyestuff of the formula and 3 percent of ammonium sulfate; the untreated part has been dyed red, while the treated part has a level light pink shade.

Example 13 Similar results are obtained when 100 parts of polyamide 6.6 yarn (Nylon yarn) are pretreated for one hour at 100 in a goods to liquor ratio 0f 1 40 with a bath containing 0.5 percent of the colourless compound given in Example 2, 2 percent acetic acid percent), and 1 percent of the auxiliary mixture given in Example the yarn is then rinsed; and otherwise dyeing is carried out as described in Examples 9 to 12.

When 1.5 percent of the above-given colourless compound are used, a stronger contrast between the light and dark shades results.

If the pretreatment is performed without the addition of the auxiliary, the contrast obtained by the subsequent dyeing is weaker.

Example 14 Polyamide 6.6 yarn (Nylon yarn) is padded with the following preparation and then squeezed out to percent weight increase:

60 parts of the colourless compound given in Example 30 parts of the ammonium salt of the acid sulphuric acid ester of the addition product of 2 mol of ethylene oxyde with 1 mol of p-tert. nonylphenol,

320 parts of a 2.5 percent aqueous solution of a starch/ether thickening, and

10 parts of acetic acid (80 percent),

made up to 1,000 parts with water. The pH-value of the preparation is 5. The fibre material is subsequently steamed for 45 minutes at 100, and then rinsed.

50 parts of pretreated polyamide yarn are combined with 50 parts of untreated polyamide yarn to a knitted fabric and dyed for 1 hour at 100 with the dyebath given in Example 8.

A usual levelling agent can be added to the dyebath in order to avoid any occurence of streakiness of the polyamide fibre material.

A knitted fabric is thus obtained having a green twotone effect.

Examples 15 27 The colourless fibre-reactive compounds given in the preceding may be replaced the following compounds:

In the following formulae, A represents hribi- QJ reactive group of the Formula I:

CH3 A A CHa (llHa AQ-A i H O a S S 0 H C H3 JHz 03H AQ-o-omorn-o-A AQ-S 02 CHa NH-C O C Ha C O O H COOH what we claim is:

fects on natural and synthetic polyamide fiber material, comprising the steps of pretreating the fiber material with an aqueous solution of a reserving agent which is a colorless fiber-reactive compound and optionally with a levelling agent having affinity for the fiber material, combining the treated fiber material with fiber material that has not been treated with said solution, and dyeing the combined fiber material with a dyestuff having affinity for the fiber material, the improvement wherein the colorless fiber-reactive compound contains at least two substituents per molecule selected from the group consisting of a substituent of formual I: NH CO R and a substituent of formula II:

N V V.

wherein R is selected from the group consistingof WW .wherein A is a substituent of formula I or formula II; B

is a direct bond, the bridge member CH=Cl-l or the bridge member D is a benzene or naphthalene radical containing at least one sulfo group; and n is an integer of 0 to 3, provided that when A is a substituent of formula II, n is l, B is CH=CH and D is 3. Process according to claim 2, wherein B represents 9. Process according to claim 4, wherein said fiberthe bridge member CH=CH, D represents a benreactive compound is of the formula zene radical containing a sulfo group, and n represents the number 1. SOBH 4. Process according to claim 1, wherein the colour- 5 less, fibre-reactive compound contains at least one A group of the Formula I. I

5. Process according to claim 4, wherein said fiberaH reactive compound is of the formula e 7 Br Br Br Br sonr 6. Process according to claim 4, wherein said fiber- 10. Process according to claim 4, wherein said fiberreactive compound is of the formula reactive compound is of the formula sent j SOaH N 1'11 1 HN-o CHN- -CH=CH 2 SO83 5 N ([JHz-(fH-CO-HN NHCOOHCH:

Br Br r r 1 03H so H N% \N a ll -NHC NII I \\N/ Hols NHCOCIPCP 11. Process according to claim 2, wherein said fiber- Br r reactive compound is of the formula 7- Process to claim wherein Said fiber-reactive 12. Process according to claim 1, which contains a compound is of the formula levelling agent having afi'mity for the fibre material.

8. Process according to claim 4, wherein said fiber- 13. Process according to claim 12, wherein the levelreactive compound is of the formula ling agent is a mixture of a. 1 part of the adduct from 1 mol of a fatty amine SOaH (30 percent of hexadecylamine, 25 percent of octa- Br Br decylamine and 45 percent of octadecenylamine) A NH-C o-oH-dm and 7 mol of ethylene oxide, quatemised with chloroacetamide, and b. 1 part of the ammonium salt of the acid sulphuric acid ester of the unquaternised adduct a. 14. Process according to claim 12, wherein the level- BY Y ling agent is employed in the dyeing of wool.

15. Process according to claim 1, in which the dyestuffs are water-soluble anionic wool dyestuffs.

16. Process according to claim 15, in which said dyestuffs contain metal.

17. Process according to claim 15, in which said dyestuffs are water-soluble azo or anthraquinone dyestuffs.

18. Process according to claim 17, in which said dye stuffs are selected from water-soluble, reactive azo or anthraquinone dyestufis which contain acyl amino substituents of a,B-unsaturated carboxylic acids having three carbon atoms.

19. Process according to claim 18, in which said dyestuffs are reactive dyestuffs which contain acyl amino substituents of a,B-unsaturated carboxylic acids having three carbon atoms and in the aor B-position a halogen atom.

20. Process according to claim 1, in which the treatment with the fibre-reactive compounds is carried out by the exhaust process at 80 to 110C, or by the impregnation process at to 40C combined with a subsequent fixing process.

21. Process according to claim 20, in which the fixation process following the impregnation process is a steaming'or cold-storage process.

22. Process according to claim 1, which contains 0.1 to l0 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material.

23. Process according to claim 1, in which wool is the natural polyamide fibre material.

24. Process according to claim 22, which contains 1 to 6 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material, for the dyeing of wool.

25. Process according to claim 1, in which said fibre is a synthetic polyamide fibre material.

26. Process according to claim 22, which contains 0.2 to 2 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material, for the dyeing of synthetic polyamide fibre material.

27. Process according to claim 1, in which the fibrereactive compounds are applied from preparations of which the pH-value is 4 to 7.

28. Process according to claim 1, in which the combining of pretreated fibre material and fibre material not pretreated is effected by mixing, carding, twisting, weaving, embroidering, or knitting.

29. Dyed polyamide fibre material having a multicolour effect, in which on at least one part of the fibre material a colourless fibre-reactive compound as re serving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least two group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourless compound.

30. Dyed mixed fibre material having a multi-colour effect, consisting in part of natural and/or synthetic polyamide fibre material, in which on at least one part of the polyamide fibre material a colourless fibrereactive compound as reserving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least one group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourless compound.

31. Mixed fibre material according to claim 30, which in addition has residual amounts present on the fibre of a levelling agent which has affinity for the fibre.

32. Mixed fibre material according to claim 31, which has residual amounts present on the fibre material of the levelling agent given in claim 13. 

2. The process of claim 1 wherein the fiber-reactive compound has the formula III: A - D - (B - D)n -A wherein A is a substituent of formula I or formula II; B is a direct bond, the bridge member -CH CH- or the bridge member
 3. Process according to claim 2, wherein B represents the bridge member -CH CH-, D represents a benzene radical containing a sulfo group, and n represents the number
 1. 4. Process according to claim 1, wherein the colourless, fibre-reactive compound contains at least one group of the Formula I.
 5. Process according to claim 4, Wherein said fiber-reactive compound is of the formula
 6. Process according to claim 4, wherein said fiber-reactive compound is of the formula
 7. Process to claim 4, wherein said fiber-reactive compound is of the formula
 8. Process according to claim 4, wherein said fiber-reactive compound is of the formula
 9. Process according to claim 4, wherein said fiber-reactive compound is of the formula
 10. Process according to claim 4, wherein said fiber-reactive compound is of the formula
 11. Process according to claim 2, wherein said fiber-reactive compound is of the formula
 12. Process according to claim 1, which contains a levelling agent having affinity for the fibre material.
 13. Process according to claim 12, wherein the levelling agent is a mixture of a. 1 part of the adduct from 1 mol of a fatty amine (30 percent of hexadecylamine, 25 percent of octadecylamine and 45 percent of octadecenylamine) and 7 mol of ethylene oxide, quaternised with chloroacetamide, and b. 1 part of the ammonium salt of the acid sulphuric acid ester of the unquaternised adduct a.
 14. Process according to claim 12, wherein the levelling agent is employed in the dyeing of wool.
 15. Process according to claim 1, in which the dyestuffs are water-soluble anionic wool dyestuffs.
 16. Process according to claim 15, in which said dyestuffs contain metal.
 17. Process according to claim 15, in which said dyestuffs are water-soluble azo or anthraquinone dyestuffs.
 18. Process according to claim 17, in which said dyestuffs are selected from water-soluble, reactive azo or anthraquinone dyestuffs which contain acyl amino substituents of Alpha , Beta -unsaturated carboxylic acids having three carbon atoms.
 19. Process according to claim 18, in which said dyestuffs are reactive dyestuffs which contain acyl amino substituents of Alpha , Beta -unsaturated carboxylic acids having three carbon atoms and in the Alpha - or Beta -position a halogen atom.
 20. Process according to claim 1, in which the treatment with the fibre-reactive compounds is carried out by the exhaust process at 80 to 110*C, or by the impregnation process at 15 to 40*C combined with a subsequent fixing process.
 21. Process according to claim 20, in which the fixation process following the impregnation process is a steaming or cold-storage process.
 22. Process according to claim 1, which contains 0.1 to 10 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material.
 23. Process according to claim 1, in which wool is the natural polyamide fibre material.
 24. Process according to claim 22, which contains 1 to 6 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material, for the dyeing of wool.
 25. Process according to claim 1, in which said fibre is a synthetic polyamide fibre material.
 26. Process according to claim 22, which contains 0.2 to 2 percent of the colourless, fibre-reactive compound, calculated on the weight of the fibre material, for the dyeing of synthetic polyamide fibre material.
 27. Process according to claim 1, in which the fibre-reactive compounds are applied from preparations of which the pH-value is 4 to
 7. 28. Process according to claim 1, in which the combining of pretreated fibre material and fibre material not pretreated is effected by mixing, carding, twisting, weaving, embroidering, or knitting.
 29. Dyed polyamide fibre material having a multi-colour effect, in which on at least one part of the fibre material a colourless fibre-reactive compound as reserving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least two group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourlEss compound.
 30. Dyed mixed fibre material having a multi-colour effect, consisting in part of natural and/or synthetic polyamide fibre material, in which on at least one part of the polyamide fibre material a colourless fibre-reactive compound as reserving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least one group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourless compound.
 31. Mixed fibre material according to claim 30, which in addition has residual amounts present on the fibre of a levelling agent which has affinity for the fibre.
 32. Mixed fibre material according to claim 31, which has residual amounts present on the fibre material of the levelling agent given in claim
 13. 